EP3050143B1 - Procédé de fabrication d'éléments électrochimiques d'une batterie solide - Google Patents

Procédé de fabrication d'éléments électrochimiques d'une batterie solide Download PDF

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EP3050143B1
EP3050143B1 EP14792373.4A EP14792373A EP3050143B1 EP 3050143 B1 EP3050143 B1 EP 3050143B1 EP 14792373 A EP14792373 A EP 14792373A EP 3050143 B1 EP3050143 B1 EP 3050143B1
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anode
cathode
electrode
accordance
modified
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EP3050143A1 (fr
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Martin FINSTERBUSCH
Chih-Long TSAI
Sven Uhlenbruck
Hans Peter Buchkremer
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Forschungszentrum Juelich GmbH
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    • H—ELECTRICITY
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    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • H—ELECTRICITY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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    • H01M10/052—Li-accumulators
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    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
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    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
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    • H01M4/387—Tin or alloys based on tin
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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    • H01M6/00—Primary cells; Manufacture thereof
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    • H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
    • H01M6/188—Processes of manufacture
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    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
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    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H—ELECTRICITY
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    • H01M2300/0017—Non-aqueous electrolytes
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    • H01M2300/0068—Solid electrolytes inorganic
    • H01M2300/0071—Oxides
    • H—ELECTRICITY
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the invention relates to the production of a solid-state battery, in particular the connection between an anode and a cathode via a non-electron-conducting electrolyte layer.
  • Li-ion batteries Rechargeable lithium-ion batteries, also referred to below as Li-ion batteries, have been flourishant in recent years. You can already find them in many mobile devices. In addition to hybrid and electric vehicles, their area of application is the possible storage of electricity from wind or solar energy systems. However, today's Li-ion batteries can not meet a number of requirements, which is why many efforts are being made to explore novel battery concepts.
  • batteries For storing electrical energy are particularly suitable electrochemical storage, which are based on the galvanic cell, colloquially called batteries. They always consist of an anode, a cathode and an electrolyte. Batteries may be intended for single use (primary battery) or reusable (secondary battery, accumulator).
  • anode and cathode which can be used for classification, the best known are probably zinc-carbon (Zn-C) batteries), alkali-manganese (alkaline) batteries, nickel cadmium (Ni -Cd) batteries, nickel-metal hydride (Ni-MH) batteries and also lead (Pb) batteries.
  • Zn-C zinc-carbon
  • alkali-manganese alkaline
  • Ni -Cd nickel cadmium
  • Ni-MH nickel-metal hydride
  • Pb lead
  • the electrolyte can be used for classification, z.
  • liquid, gel or polymer electrolytes can be used in Li-ion batteries.
  • Today's standard battery types contain almost exclusively liquid or gelatinous electrolytes.
  • a new type of battery which inherently does not possess the aforementioned safety risks and is thus clearly superior to the conventional types in this respect, is the type of solid-state battery or solid-state electrolyte battery.
  • Electrolytes instead of the normally liquid or polymer-stabilized (gel) Electrolytes used an ion-conducting solid. This can be both organic (polymers, etc.) or inorganic (ceramics, glasses, etc.). Decisive for the functionality of an electrolyte is the low electronic conductivity while high ionic conductivity and (electro) chemical stability compared to the anode and cathode material.
  • inorganic solid-state ionic conductors examples include z. B. yttrium stabilized zirconia or gadolinium stabilized ceria, which can conduct oxygen ions and can be used for metal - metal oxide high temperature batteries as electrolyte, which have a similar structure as an oxide ceramic fuel cell. Further examples are ⁇ -alumina, which can guide sodium ions and is used in Na-liquid metal batteries, and lithium-phosphorus-oxy-nitrite (LIPON), which can conduct lithium ions and is used in lithium thin-film batteries.
  • LIPON lithium-phosphorus-oxy-nitrite
  • LiFePO 4 cathode Li 7 La 3 Zr 2 O 12 electrolyte and a Si anode
  • a thin-film battery of similar construction which is sold by the company Infinite Power Solutions and the brand name Thinergy®.
  • High-temperature sodium batteries, with the abovementioned alumina solid electro-lyte, are already marketed by Fiamm Sonick for use in electric vehicles.
  • the cathode and anode comprise a single- or multi-phase mixture.
  • the phases are, for example, a first phase a, comprising the active material for ion deposition and removal, a second phase b, comprising the material for ionic conduction, and a further phase c, which comprises a material having an electronic conductivity ,
  • a further phase c which comprises a material having an electronic conductivity
  • one or more functions may also be taken over by a material of another phase.
  • the individual phases can - must but not - are present in the same state of aggregation and are referred to below as mixed conducting electrodes.
  • anodes and cathodes are each separated by an electrolyte, which is a non-electronically conductive layer but has the highest possible ion conductivity.
  • electrolyte which is a non-electronically conductive layer but has the highest possible ion conductivity.
  • this is done by an additional porous, non-electron or ion-conducting, electrolyte-impregnated separator, which among other things serves for the spatial separation of the liquid-saturated anode and cathode.
  • This spatial separation should advantageously be kept as thin as possible in order to keep the total internal resistance of the cell as low as possible.
  • Exemplary embodiments of such solid-state batteries or batteries with solid-state electrolytes from industry are known, but hitherto even more a niche segment due to complicated production methods and thus high costs (per unit capacity).
  • a lithium based commercial solid-state thin film cell is marketed by the company "Infinite Power Solutions” under the name “Thinergy® MEC200”.
  • Thininergy® MEC200 Each component of the cell is produced by a complex gas phase process. On This type can be realized only thin electrodes, which greatly affects the total capacity of the cell.
  • the object of the invention is to provide a new method for producing a solid-state battery, which provides a very thin, ion-conducting, but electrically insulating layer as an electrolyte between an anode and a cathode of a battery cell, and is simple and / or inexpensive.
  • solid-state battery in the following description of the invention, this includes both primary batteries and secondary batteries.
  • the basic idea of the invention is based on dispensing with the incorporation or application of a separate electrolyte layer in the production of a solid-state battery, but rather directly utilizing the ionically conductive phase contained in the mixed-conducting electrodes for electronic separation of the electrodes.
  • a new process step is proposed in which the surface of at least one of the prepared or prepared mixed-conducting electrodes is modified to a certain depth such that the electronic conductivity in this modified region is markedly reduced or reduced is completely reduced.
  • the existing ionic conductivity in this surface area should be impaired as little as possible.
  • the area modified in this way can then advantageously assume the function of an electrolyte layer.
  • the typical mixed-conducting electrodes which are designed to conduct both electrons and ions, and which can be produced or used in the context of this invention, generally comprise a mono- or multiphase mixture.
  • the purpose of the invention modification of the upper surface of an electrode by an additional treatment is to change a near-surface region of one or both electrodes such that this region or the areas can take over the function of an electrolyte or can.
  • the aim of the modification is thus to reduce the electronic conductivity in the surface region of a mixed-conducting electrode to such an extent that after the assembly of anode and cathode, a functional battery is provided, wherein the modified surface area of at least one of the two electrodes good ions conductive, but poorly electronically conductive is.
  • the inventively modified surface area thereby prevents a direct electronic contact between the electrodes and thus a short circuit.
  • the term "poorly electronically conductive” is understood to mean an electronic conductivity of less than 1 ⁇ 10 -8 S / cm. This value is at the upper limit in order to regularly prevent an electronic short circuit between the anode and the cathode. However, an electronic conductivity of less than 1 ⁇ 10 -10 S / cm is advantageous. However, since the electrolyte layer should be made as thin as possible, even smaller electronic conductivities down to the range of 1 ⁇ 10 -12 S / cm or even less are particularly desirable for this modified region.
  • the additional treatment method should simultaneously have the property of not adversely affecting the ionic conductivity of the modified surface area of the previously mixed-conducting electrode advantageous.
  • the modified surface area should have the ionic conductivity which is usually necessary for an electrolyte, in the case of a Li-ion battery of at least 10 -6 S / cm, but advantageously at least 10 -4 S / cm, and more preferably even more than 10 -2 S / cm.
  • the ionic conductivity of the modified surface area required in each case for a solid-state battery also depends, inter alia, on its layer thickness, since a particularly thin layer thickness can partially compensate for less good ionic conductivity.
  • an additional treatment method by a chemical reaction is the heating in oxygen, air or ozone to call, the ozone etching by means of a plasma and the treatment of the surface with an oxidizing acid, with the z. B. carbon can be modified.
  • phase transformation are laser treatment of the surface in an inert atmosphere, such as He or Ar, or heating the surface by means of a He or Ar plasma.
  • the depth to which the electronic conductivity of the electrode must be destroyed by the additional treatment depends on various parameters. The most important here is the electronic conductivity of the electrolyte layer itself produced by the modification of the electrodes. For the functioning as a solid-state battery, a sufficiently low self-discharge should be ensured. Values for the electronic conductivity of the electrolyte or the modified surface area of maximally 1 ⁇ 10 -8 S / cm are desirable, whereby a value around 1 ⁇ 10 -10 S / cm is better and a value around or smaller than 1 ⁇ 10 -12 S / cm is particularly advantageous. The further the electronic conductivity can be reduced by the additional treatment in the modified area of the mixed conductor, the lower the layer thickness up to which the treatment must reach can be selected.
  • the electrode area A and the predetermined maximum self-discharge current I, the depth d of the area to be treated is a function of the electronic conductivity ⁇ achieved by the treatment.
  • d AU I ⁇
  • the necessary layer thicknesses for the modified surface area in total are thus typically in the range from 1 nm to a few tens of ⁇ m.
  • the common ceramic powders which are suitable for producing a mixed-conducting electrode have a particle size range between 1 nm and 1 mm. Useful or relevant for most conventional applications here is the sub-range of 10 nm to 100 microns. A particularly advantageous range could be around the 1 ⁇ m grain size, but this can vary depending on the specific requirement of an application.
  • the power density is inversely proportional to the grain size of the anode or cathode active material, i. E. H. smaller grains - larger, or higher discharge currents (small capacity), while the energy density is proportional to the grain size of the anode or cathode active material, d. H. larger grains - low discharge currents (high capacity).
  • the surface of the thus treated electrode is treated by the method according to the invention such that the electronic conductivity on the surface of the electrode is destroyed, or significantly reduced, but not the ionic conductivity.
  • this treated surface area can now perform the function of an electrolyte. It may optionally, but not necessarily, be modified in the same or a second step, the active material.
  • the modification of the active material for example, be necessary if the active material itself also has a not inconsiderable electrical conductivity.
  • the cathode material LiCoO 2 has a relatively good electrical conductivity
  • FePO 4 has only a very low electrical conductivity as the cathode material.
  • the two mixed-conducting electrodes that is, both the anode and the cathode, subjected to an additional treatment, so that both electrodes subsequently have a surface area with significantly reduced electronic conductivity.
  • the aforementioned estimates relating to the necessary layer thickness of the modified regions, which then form the electrolyte layer logically refer to the sum of the individual modified layer thicknesses of anode and cathode.
  • the modification of the surface of both the anode and the cathode by means of an identical method and the determined necessary layer thickness is advantageously divided in half on the anode and cathode. This would have the further advantage that the process settings can be maintained almost identical, regardless of whether the surface of an anode or a cathode is to be modified.
  • the anode and the cathode are brought together and connected in a suitable manner.
  • the functionality should be preserved, that a hike of the Ions in the battery to be produced by this interface is possible.
  • the electronic connection must not be restored, ie a short circuit must be avoided.
  • a material-specific, new or already known method can be used.
  • the compound can be made simply by sintering at elevated temperatures.
  • the cell thus produced can then be further processed into a cell composite and the actual solid-state battery.
  • the assembly of the solid state battery is carried out such that at least one of the thus treated surfaces of the anode and / or the cathode is located as a boundary region between the electrodes and thus assumes the function of the electrolyte. In this way, the mixed-conducting anode and the mixed-conducting cathode are separated from each other electronically, but the ion conduction still remains.
  • the assembly is preferably such that both treated surfaces of the anode and the cathode are disposed adjacent, and thus located between the electrodes. Both treated surfaces together take over the function of the electrolyte.
  • a series connection of these cells thus produced can be carried out, wherein an anode / cathode unit of a cell is brought together directly or via a current collector with the next cathode / anode unit until the desired number of repeating units for the stack is reached.
  • Another embodiment of the invention takes account of the fact that, if appropriate, very different materials are used for the ionic or electronic conductivity in anode and cathode.
  • materials with significantly different conductivity can be used.
  • different active materials can be used, wherein a material z. B. has a much higher capacity.
  • sandwich unit of z. B. 2 cathodes outside with an anode in the middle (or vice versa) conceivable. Depending on the design, this usually results in advantages in the power density or the energy density.
  • the sandwich unit can be provided in particular as a three-pole design.
  • the cells produced in this way can also be brought together in the form of a series connection directly or via current collectors with the next sandwich unit until the desired number of repeat units for the stack has been reached.
  • connection between the anode and cathode can optionally also be carried out with the aid of further process steps or additional materials, for example to suppress the restoration of the electrical connection and / or to facilitate the ion transfer at the interface.
  • the production of a particularly good compound may, for example, also include the use of additives in the mixed-conducting electrodes or an additional application of so-called sintering aids (or catalysts, fluxes, etc.) at the interface.
  • additives in the case of Li 7 La 3 Zr 2 O 12 (LLZ) as a phase of the electrode, it is advantageous to use Li salts as additives which form a melt, or other oxides having a lower melting point, such as. B. Li 3 BO 3 .
  • This also includes mechanical or chemical process steps which are used to optimally connect the surfaces of the anode and cathode, such as, for example, prior roughening or prior heating of the interfaces, as well as fixation under pressure.
  • the method according to the invention advantageously makes possible a production process for a solid-state battery in which an hitherto mostly expensive and complicated thin-film process for a separate electrolyte is replaced by at least one of the electrodes for a substantially simpler surface treatment process.
  • Suitable active materials for a mixed-conducting cathode for a Li-ion battery (commercially available), which can be used in the inventive method: cathode material LiCoO 2 LiMn 2 O 4 Li (NiCoMn) O 2 LiFePO 4 Reversible capacity (mAh / g) 140 100 150 145 Working voltage (V) 3.6 3.8 3.8 3.2 Energy density of the battery (Wh / kg) 180 100 170 130
  • Suitable active materials for sodium ion batteries include: NaFePO 4 , NaCoO 2 , Na 2/3 [Ni 1/3 Mn 2/3 ] O 2 , NaVPO 4 F, Na 3 V 2 (PO 4 ) 3 .
  • Suitable active materials for a mixed conducting anode for a Li-ion battery which can be used in the inventive method: anode material limiting compound medium voltage vs. Li + / Li (V) theor. spec. Capacity (mAh / g) theor. Capacity density (Ah / L) Volume expansion on reaching theoretical capacity (%) Carbon based LiC 6 0.1 374 760 12.8 Zinnbasiert Li 4 . 4 Sn 0.4 992 7240 260 Silicon - based Li 4.4 Si 0.3 4200 9660 310 Li 4 Ti 5 O 12 Li 7 Ti 5 O 12 1.5 175 610 ⁇ 1
  • Suitable active materials for sodium ion batteries include: carbon, sodium metal, as far as compatible with the electrolyte to be produced, and Na 2 Ti 6 O 13 related materials.
  • the materials suitable as solid electrolyte materials for sodium ion batteries such as ⁇ - or ⁇ "-alumina or Na 1 + x Zr 2 Si x P 3x O 12 (0 ⁇ x ⁇ 3) (NASICON materials) may also be mentioned ,
  • Cathode Active Material NaFePO 4 at 154mAh / g and ca. 2.8V vs. C anode at 187mAh / g and a ⁇ -Al 2 O 3 solid electrolyte.
  • the depth to which the electronic conductivity must be destroyed or significantly reduced depends on various parameters. The most important here is the electronic conductivity of the electrolyte produced by the modification of the electrodes themselves. It is necessary to ensure a sufficiently low self-discharge. In this case, values for the electronic conductivity of the electrolyte or the modified surface of ⁇ 1 ⁇ 10 -8 S / cm are desirable, whereby a value of 1 ⁇ 10 -12 S / cm is to be regarded as particularly advantageous.
  • the value of the self-discharge current here was estimated to be 0.6 ⁇ A, since 5% of the maximum capacity per month is a typical value for self discharge with good lithium polymer (batteries for MP3 players, cameras, etc.).
  • the particle sizes of the suitable common ceramic powders are regularly in the range between 1 nm and 1 mm. Useful or more relevant here is the subrange of 100 nm to 100 ⁇ m for most conventional applications. An optimum range could be around the 1 ⁇ m grain size, but this can vary depending on the specific requirement of an application.
  • the electronically conductive phase should be destroyed for each electrode, for example, each 2.5 microns deep, or reduced to the appropriate predetermined value. This is a realistic value with the desired particle size of about 1 ⁇ m of the LLZ matrix.
  • the thermal treatment may be mentioned, in which, for example, carbon, burned as an electrically conductive phase, by heating to temperatures above 600 ° C in an oxygen-containing atmosphere.
  • the surface can be carried out, for example, in a conventional oven or a halogen oven with high heating rate, in which air or oxygen is injected, or by means of a laser irradiation in air and regularly leads to burning out of the carbon from the surface region, wherein in particular the exposure time Depth of discharge determined.
  • the electrolyte material (ionic conductive phase) Li 7 La 3 Zr 2 O 12 (LLZ) decomposes, however, only from> 1250 ° C and is thus not affected.
  • the temperature could be increased even further, for example to 800 ° C.
  • the active material LiFePO 4 (LFP) could be decomposed in the cathode and thus additionally possible short circuits on the active material can be prevented.
  • An alternative to the aforementioned method could also be the dissolution of the carbon by means of a strong oxidizing acid, for. B. with the aid of sulfuric acid (optionally hot sulfuric acid) or nitric acid.
  • the end product when using nitric acid would be (6 (CO 2 H) 6 C), which can be additionally used as a catalyst V 2 O 5 in order to increase, for example, mellitic the reaction.
  • an electrochemical oxidation of the carbon is possible, for. B. with the aid of hydroxide melts (LiOH, KOH or NaOH) and applying a voltage, as in alkaline fuel cells (AFC) or direct carbon fuel cell (DCFC) is known. Again, current strength and exposure time the layer depth of the oxidation determine. (Operating temperature around 700 ° C, graphite in the mixing electrodes acts as anode and "fuel", typical current densities around 100 mA / cm 2 at 0.45 V).
  • the two previous methods are incompatible with the electrolyte material used, for example, because the electrode has a different material than Li 7 La 3 Zr 2 O 12 (LLZ), z.
  • LLZ Li 7 La 3 Zr 2 O 12
  • the carbon for example, can be removed gently by means of an ozone purification.
  • Such a method finds similar use in Si-wafer cleaning in the industry. Since carbon is also frequently used as electrical phase in mixed-conducting anodes, the same method can also be advantageously used for the treatment of an anode.
  • the electrode on the non-modified surfaces can be protected by providing these surfaces with a protective layer, for example an additional graphite layer.
  • a protective layer for example an additional graphite layer.
  • the electrode in the case of a treatment with a liquid reagent, the electrode can be immersed in the liquid only with the surface to be modified, or the surface to be modified is wetted only superficially with the liquid.
  • both mixed-conducting electrodes have the same phase which is responsible for the electronic conductivity, it may be possible to use the same method for the reduction of the electronic conductivity on the surface of both the cathode and the anode. This could be industrially advantageous from a process speed standpoint.
  • the treatment of a double surface to a defined depth could be more advantageous than the treatment of only one surface but then to twice the depth.
  • the other phases, ie the active material and the ionic conductive phase, of the two electrodes are compatible with the chosen surface method, it is advantageous to use the same methods for both electrodes. Otherwise, in order to obtain the aforementioned process speed advantage, two different surface treatment methods may have to be chosen, which could potentially lead to higher investment costs.
  • anode and cathode to be used have two different materials for the electronic conductivity, or if one of these phases has two properties which can not be influenced independently of one another, it may possibly be appropriate to treat only one of the mixed-conducting electrodes.
  • examples of Li 7 La 3 Zr 2 O 12 (LLZ) matrices which could also occur after the modification according to the invention of a surface of a mixed-conducting anode and cathode, were placed on top of each other and without pressure at 1200 ° C. for 35 hours sintered in air.
  • an equal sample of LLZ matrix was taken.
  • the conductivity of the sample was investigated by the interface and how it changes as a result of the contacting. As a result, it was found that the total conductivity was reduced by only 1.5 to 5.8 ⁇ 10 -5 S / cm from 8.8 ⁇ 10 -5 S / cm as compared with the same-size continuous comparative sample.
  • E m characterizes the modified surface area of the electrode E and E ' m the modified surface area of the counter electrode E'. With CC pantographs are marked.
  • FIGS. 3 and 4 Possible modifications or arrangement variants are shown in the form of a sandwich unit which, for certain material systems, regularly yields advantageously higher voltages or current densities and thus higher energy densities or power densities.
  • the surface treatment ideally does not alter the ion-conducting phase, thus preserving the structure at the later assembly site. If this is not changed during the final assembly of the mixed-conducting anode and cathode, this area can optionally be easily identified by suitable microscopy methods. In this case, the different contrast of the modified or the complete absence of the electrically conductive phase in the otherwise unmodified matrix of the ionically conducting phase could be exploited.

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Claims (12)

  1. Procédé de fabrication d'au moins un élément électrochimique d'une batterie solide, comprenant une anode de conduction mixte, une cathode de conduction mixte ainsi qu'une couche électrolytique disposée entre anode et cathode, avec les étapes consistant à :
    - préparer ou fournir une anode de conduction mixte,
    - préparer ou fournir une cathode de conduction mixte,
    - modifier la surface d'au moins l'une des deux électrodes par une étape de procédé supplémentaire de telle sorte que, dans une couche de l'électrode proche de la surface à température ambiante, la conductivité électronique perpendiculairement à l'élément est abaissée à moins de 10-8 S/cm, alors que la conductivité ionique est supérieure à 10-6 S/cm,
    - dans lequel la modification de la surface d'au moins une électrode se fait par une réaction chimique avec un réactif liquide, gazeux ou solide ou par une transformation physique de phase,
    - rassembler ensuite l'anode et la cathode pour donner une batterie solide de telle sorte que la couche modifiée en surface d'au moins une électrode est disposée à la limite entre l'anode et la cathode en tant que couche électrolytique, et que les électrodes de conduction mixte sont ainsi séparées électroniquement.
  2. Procédé selon la revendication précédente, dans lequel une anode comprenant LiC6, Li4,4Sn, Li4,4Si, LiTi5O12, Na2Ti6O13Na ou le métal Li comme matériau actif - est utilisée.
  3. Procédé selon l'une des revendications 1 à 2, dans lequel une cathode comprenant LiCoO2, LiMn2O4, Li(Ni,Co,Mn)O2, LiFePO4, LiNixCo1-xO2, LiNixMn2-xO4, NaFePO4, NaCoO2, Na2/3 [Ni1/3Mn2/3]O2, NaVPO4F ou Na3V2(PO4)3 comme matériau actif est utilisée.
  4. Procédé selon l'une des revendications 1 à 3, dans lequel la modification de la surface d'au moins une électrode s'effectue par une réaction chimique de l'électrode avec un réactif liquide.
  5. Procédé selon l'une des revendications 1 à 3, dans lequel la modification de la surface d'au moins une électrode s'effectue par une réaction chimique de l'électrode avec un solide.
  6. Procédé selon l'une des revendications 1 à 3, dans lequel la modification de la surface d'au moins une électrode s'effectue par une réaction chimique de l'électrode avec un réactif gazeux.
  7. Procédé selon l'une des revendications 1 à 3, dans lequel la modification de la surface d'au moins une électrode s'effectue par une transformation physique de phase.
  8. Procédé selon l'une des revendications 1 à 7, dans lequel les deux surfaces d'électrode sont modifiées.
  9. Procédé selon l'une des revendications 1 à 8, dans lequel l'épaisseur de couche de la surface modifiée ou des surfaces modifiées atteint au total, lors de leur assemblage, une épaisseur de couche d'au minimum 0,1 nm et d'au maximum 100 µm, en particulier une épaisseur de couche comprise entre 0,1 µm et 10 µm.
  10. Procédé selon l'une des revendications 1 à 9, dans lequel la modification de la surface d'au moins une électrode à température ambiante permet d'abaisser la conductivité électronique perpendiculairement à l'élément jusqu'à moins de 10-9 S/cm et avantageusement jusqu'à moins de 10-12 S/cm.
  11. Procédé selon l'une des revendications 1 à 10, dans lequel un additif est incorporé à l'interface lors de l'assemblage des deux électrodes avec au moins une couche modifiée proche de la surface.
  12. Procédé selon l'une des revendications 1 à 11, dans lequel la conductivité ionique à température ambiante, après la modification de la surface dans cette zone, est d'au moins 10-4 S/cm, en particulier néanmoins supérieure à 10-2 S/cm.
EP14792373.4A 2013-09-27 2014-09-05 Procédé de fabrication d'éléments électrochimiques d'une batterie solide Active EP3050143B1 (fr)

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DE102013017594.1A DE102013017594A1 (de) 2013-09-27 2013-10-22 Herstellungsverfahren für elektrochemische Zellen einer Festkörperbatterie
PCT/DE2014/000460 WO2015043564A1 (fr) 2013-09-27 2014-09-05 Procédé de fabrication d'éléments électrochimiques d'une batterie solide

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JP6984185B2 (ja) * 2017-06-08 2021-12-17 株式会社Ihi 正極活物質、正極及びナトリウムイオン電池、並びに、正極活物質の製造方法
US11664532B2 (en) 2017-08-24 2023-05-30 Fraunhofer-Gesellschaft Zur Foerderung Der Angewandten Forschung E.V. Solid-state battery based on an ion-conductive matrix composed of camphor or 2-adamantanone
KR102148512B1 (ko) * 2017-09-01 2020-08-27 주식회사 엘지화학 양극 활물질의 제조방법 및 이를 이용한 양극 활물질 및 리튬 이차전지
DE102018210120A1 (de) 2018-06-21 2019-12-24 Bayerische Motoren Werke Aktiengesellschaft Spiral-Festkörperzelle
KR20200053998A (ko) 2018-11-09 2020-05-19 삼성전자주식회사 금속-공기 전지
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DE102019132370B4 (de) 2019-11-28 2021-11-11 Forschungszentrum Jülich GmbH Semi-interpenetrierende Polymernetzwerke auf Basis von Polycarbonaten als Separatoren für den Einsatz in Alkali-Metall-Batterien und damit hergestellte Alkali-Metall-Batterien

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ES2646124T3 (es) 2017-12-12
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PL3050143T3 (pl) 2017-12-29
WO2015043564A1 (fr) 2015-04-02
DE102013017594A1 (de) 2015-04-02
JP2016532244A (ja) 2016-10-13
EP3050143A1 (fr) 2016-08-03
JP6637412B2 (ja) 2020-01-29
CN105556719B (zh) 2020-04-07
US10763549B2 (en) 2020-09-01
US20170263980A1 (en) 2017-09-14

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